Enhancement of antiferromagnetic interaction and transition temperature in M<Subscript>3</Subscript>TeO<Subscript>6</Subscript> systems (M = Mn,Co, Ni,Cu)

Several M₃TeO₆ (M = Mn, Co, Ni, Cu) oxides order antiferromagnetically at low temperatures (?60 K), while displaying interesting dielectric properties at high temperatures (ferroelectricity below 1000 K in M = Ni case). We have investigated and analyzed the structural and magnetic properties of Mn-doped Co₃TeO₆ and Ni₃TeO₆, which order antiferromagnetically at temperatures higher than their undoped counterparts.     

Features of Electronic Structure of Intermetallic Compounds CeNi<Subscript>4</Subscript>M (M = Fe,Co, Ni,Cu)

The evolution of the electronic structure of CeNi₄M (M = Fe, Co, Ni, Cu) intermetallics depending on the type of nickel substitutional impurity is explored. We have calculated band structures of these compounds and considered options of substituting one atom in nickel 3d sublattice in both types of crystallographic positions: 2c and 3g. The analysis of total energy self-consistent calculations has shown that positions of 2c type are more energetically advantageous for single iron and cobalt impurities, whereas a position of 3g type is better for a copper impurity. The Cu substitutional impurity does not change either the nonmagnetic state of ions or the total density at the Fermi level states. Fe and Co impurities, on the contrary, due to their considerable magnetic moments, induce magnetization of 3d states of nickel and cause significant changes in the electronic state density at the Fermi level.     

NMR study of the electric field gradient in the paramagnetic phase of M<Subscript>3</Subscript>V<Subscript>2</Subscript>O<Subscript>8</Subscript> (M = Co,Ni) compounds

The NMR spectra and the decay of a spin echo signal from ⁵¹V nuclei in Kagome-staircase Co₃V₂O₈ (CVO) and Ni₃V₂O₈ (NVO) single crystals are measured in the temperature range 30–300 K and a magnetic field H ₀ = 20 kOe. The orientation dependences of the ⁵¹V NMR line shape are used to determine the electric field gradient (EFG) parameters, namely, quadrupole frequency ν _Q and asymmetry parameter η. These parameters for NVO and CVO are ν _Q = 180(10) kHz, η = 0.5(1) and ν _Q = 130(10) kHz, η = 0.6(1), respectively. A comparison of the results of calculating EFG tensors with a point charge model and the NMR data indicates that the crystallographically equivalent vanadium atoms in the Ni₃V₂O₈ and Co₃V₂O₈ compounds differ in the EFG axis orientation. M₃V₂O₈ crystals are found to have vanadium positions (V1, V2) with different orientations of the z axis, which specifies the direction of the principal value of EFG (V _zz ): these orientations lie in the bc plane and make an angle of either +51(5)° (V1) or −51(5)° (V2) with axis c. In the temperature range 30–300 K, the EFG tensor components and the local symmetry of the charge surrounding of the vanadium positions in NVO and CVO oxides are found to change insignificantly.     

Synthesis and characteristics of Fe<Subscript>96-x</Subscript>Zr<Subscript>x</Subscript>B<Subscript>4</Subscript> nanowire arrays

Fe-rich Fe_96-xZr_xB₄ (0≤x≤7) nanowires were first prepared by electrodepositing into anodic aluminum oxide templates. Transmission electron microscope analysis shows that the nanowires are uniform and are about 100 nm in diameter with an aspect ratio of around 75. The broad peaks of X-ray diffraction and the Mössbauer spectrum indicate that the Fe_96-xZr_xB₄ nanowires are composed of α-Fe-like and Zr-rich FeZrB phases. Selected area electro diffraction results also indicate that the structure of Fe₈₉Zr₇B₄ nanowires is amorphous. A vibrating sample magnetometer is employed to study the magnetic properties of nanowire arrays at room temperature. The coercivity of nanowire arrays in parallel to the wire axis decreases with increasing Zr content.     

One-dimensional Bi<Subscript>2</Subscript>Mo<Subscript>x</Subscript>W<Subscript>1-x</Subscript>O<Subscript>6</Subscript> sosoloids: controllable synthesis by electrospinning process and enhanced photocatalytic performance

One-dimensional Bi₂Mo_xW_1-xO₆ (x = 0, 0.2, 0.5, 0.67, and 1) photocatalysts have been successfully synthesized for the first time by a straightforward electrospinning technique with a calcination process. The as-formed Bi₂Mo_xW_1-xO₆ nanofibers are composed of inter-linked nanosheets of 30–50 nm in size and characterized by thermogravimetric and differential scanning calorimetric, Fourier transform infrared, Raman spectra, X-ray powder diffraction, scanning electron microscope, Brunauer-Emmett-Teller, transmission electron microscope, UV-Vis spectroscopy, photoluminescence, HPLC, and EIS. The photodegradation behaviors towards organic dyes, including rhodamine B (RhB) and methylene blue (MB) are investigated, and the results illustrate that Bi₂Mo_0.25W_0.75O₆ nanofibers exhibit the highest photocatalytic performance under visible light irradiation than Bi₂Mo_xW_1-xO₆ (x = 0, 0.2, 0.5, 0.67, and 1) samples. The possible mechanisms of the enhanced photocatalytic properties are discussed in detail.     

Relations between physical properties of the biferroic Pb(Fe<Subscript>1-x</Subscript>Nb<Subscript>x</Subscript>)O<Subscript>3</Subscript>ceramics and their composition change

The work shows basic features of ferromagnetic ceramics Pb(Fe_{1 - x}Nb_x)O₃ with various contents of Fe/Nb (x=1/3, 1/2, 2/3). The synthesis were carried out by powders sintering and calcination whereas densification by hot uniaxial pressing and conventional sintering methods. Optimum conditions of PFN obtention with various contents were based on X-ray, microstructural, dielectrical and conductivity tests together with increase of iron contents in Pb(Fe_{1 - x}Nb_x)O₃ usage parameters of those ceramics worsen. Optimum parameters are shown by the ceramics with contents Pb(Fe_{1 / 2}Nb_{1 / 2})O₃ synthetized using calcination method and densified by hot uniaxial pressing method.     

Synthesis and application of nanostructured MCo<Subscript>2</Subscript>O<Subscript>4</Subscript>(M=Co,Ni) for hybrid Li-air batteries

We report the synthesis of MCo₂O₄ (M=Co, Ni) on Ni-mesh by a simple metal acetate decomposition method. Stability tests of the samples in aqueous acidified LiCl, LiOH and LiTFSI in H₂O/DME showed that Co₃O₄/Ni and Co₃O₄-PVP/Ni are relatively stable in alkaline and neutral environments, with Co₃O₄/Ni being relatively more stable. For NiCo₂O₄/Ni and NiCo₂O₄-PVP/Ni, the low weight percentage change of cobalt in LiTFSI in H₂O/DME suggests that they are mostly stable in this electrolyte. The electrochemical performance of the Li-air cell was evaluated using Li anode and a LAGP ceramic separator with above mentioned electrolytes. Co₃O₄ showed slightly higher catalytic activity for oxygen reduction reaction (ORR) than for oxygen evolution reaction (OER) for the first three cycles. The cell with LiTFSI in H₂O/DME as aqueous catholyte showed that NiCo₂O₄ is a better catalyst for the OER than for the ORR, while the reverse was observed when LiOH was used as the electrolyte.     

Controlled-synthesis,characterization, and magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanostructures

Fe₃O₄ nanostructures with different morphologies, including uniform nanoparticles, nanorods and nanowire bundles, have been successfully synthesized via a facile hydrothermal route. Based on the observation of TEM images, the growth mechanism of one-dimensional Fe₃O₄ nanostructures is in accordance with Ostwald ripening process. From the hysteresis loops of as-prepared Fe₃O₄ products, we found that the morphology has great influence on the magnetic properties. The uniform Fe₃O₄ nanoparticles have higher saturation magnetization and lower coercivity than that of Fe₃O₄ nanorods and nanowires bundles. These phenomena attribute to the high shape anisotropy of nanorods and nanowire bundles, which prevent them from magnetizing in directions other than along their easy magnetic axes. PACS 81.07.-b; 75.50.Bb; 75.30.Gw; 81.10.Dn; 81.16.Be     

Half-metallicity and magnetism of the quaternary inverse full-Heusler alloy Ti<Subscript>2-x</Subscript>M<Subscript>x</Subscript>CoAl (M = Nb,V) from the first-principles calculations

Using the first-principles calculations based on density functional theory, we investigate the more d-electrons doping effects on the electronic structure and magnetism of the parent inverse Heusler alloy Ti₂CoAl by the substitution of Nb and V atoms for Ti(A) and Ti(B) atoms locating at the two inequivalent sublattices. The Ti₂CoAl is half-metallic with Fermi level near the top of the minority-spin valence band and hence its spin-polarization is easily reduced by the spin-flip excitation. Our total energy calculations show that the V/Nb doping at the Ti(A)/Ti(B) site is energetically favorable compared with the Ti(B)/T(A) site due to the lower total energy. Our band structure calculations indicate that for the V doped compounds, half-metallicity can be well retained regardless of doping sites and percentages except for the case of Ti(A)-site doping with x = 1, while for Nb doped compounds, the half-metallicity persists only in Ti(B)-site doping with different percentages. For the doped compounds with half-metallicity, the Fermi level shifts from the top of minority-spin valence band to the bottom of minority-spin conduction band with increasing content of x, and typically, the doped compounds (V in Ti(A) and Ti(B) sites at x = 0.75 and 0.5, respectively; Nb in Ti(B) site at x = 0.5), whose Fermi levels are adjusted to the expected positions to effectively inhibit the spin-flip excitation are promising candidates for spintronics applications.     

Synthesis and studies of trisubstituted biphthalonitrile/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic hybrid microspheres

New trisubstituted biphthalonitrile/magnetite (TSB/Fe₃O₄) magnetic hybrid microspheres were synthesized from TSB and FeCl₃ · 6H₂O using the method of one-stage thermal temperature crystallization of solvents. The morphology and structure of magnetic hybrid microspheres were inspected using a scanning electron microscope, IR Fourier spectroscopy, and X-ray diffraction. It was found that the grown TSB/Fe₃O₄ magnetic hybrid microspheres represent spherical particles with an average size of ~137 nm and a small size spread. The size and size distribution of magnetic hybrid microspheres can be controlled by a small change in the ratio of TSB and Fe³⁺ ion contents in the microsphere. TSB/Fe₃O₄ hybrid microspheres exhibit a rather high saturation magnetization (58.16 emu g^–1) and new microwave electromagnetic properties, i.e., lower (in comparison with published) dielectric losses at low frequencies; magnetic losses are increased obviously due to an increase in the TSB content. Furthermore, it is detected that magnetic hybrid microspheres absorb microwaves, and strong reflection losses in a wide frequency range are established. The effective reflection loss of–31 dB is obtained in the microwave range from 2 to 16 GHz due to TSB content variations. Wide absorption properties of microwaves along with regular spherical shape and excellent magnetic properties offer wide opportunities for various applications of TSB/Fe₃O₄ magnetic hybrid microspheres as functional materials.     

Genesis,structural, and transport properties of La<Subscript>2</Subscript>Mo<Subscript>2-x</Subscript>W<Subscript>x</Subscript>O<Subscript>9</Subscript> prepared via mechanochemical activation

Fast oxide-ion conductors La₂Mo_2-xW_xO₉ (x = 0–1) have been prepared using mechanochemical activation (MA) of starting oxides in a high-power planetary ball mill. Studies of La₂Mo_2-xW_xO₉ genesis and structural properties using thermal analysis, XRD, SEM, IR, and Raman spectroscopy have revealed that MA results in the formation of an amorphous precursor, while the cubic β-phase is formed after calcination at 700–900 °C. Due to a high dispersion of powders, high-density pellets of W-LAMOX ceramics have been obtained already after sintering at 950 °C. Their electrical conductivity measured by the impedance spectroscopy depends on the W concentration being sufficiently high (up to 5.6?10^?3 S/cm at 630 °C) at temperatures below 650 °C.     

Synthesis and Luminescent Properties of M<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript>: Eu (M=Sr,Ba) Nanophosphors

A solution combustion route for the synthesis of Eu³⁺-activated M₂V₂O₇ (M = Sr, Ba) and their luminescent properties have been investigated. Structure and luminescent characteristics of Sr₂V₂O₇:Eu³⁺ and Ba₂V₂O₇:Eu³⁺ nanophosphors have been studied by x-ray diffraction, scanning electron microscopy, transmission electron microscopy, fluorescence spectrometry and Fourier transform infra-red spectroscopy. The incorporation of Eu³⁺ activator in these nanoparticles has been checked by luminescence characteristics. These nanoparticles have displayed red color under a UV source which is due to characteristics transition of Eu³⁺ from ⁵D₀ → ⁷F₂ at 613 nm in both Sr₂V₂O₇:Eu³⁺ and Ba₂V₂O₇:Eu³⁺ nanophosphors. In addition, the optimal Eu³⁺ - doped contents of Sr_2(1-x)Eu_2xV₂O₇ and Ba_2(1-x)Eu_2xV₂O₇ nanophosphors for both were 4 mol%.     

Mössbauer studies of magnetic Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/SiO<Subscript>2</Subscript> nanocomposites

A large variety of glass and glass ceramics may be obtained by sol-gel process from hydrolysis of tetraethoxysilane. The transformation involves hydrolysis and polycondensation reactions leading to the growth of clusters that eventually collide together to form a gel. The structure and properties of the final product have been found to be strongly dependent on the initial conditions of preparation. Silica nanocomposites based on Fe₂O₃/SiO₂ were prepared with the help of ultrasonic activation and subsequent annealing in nitrogen atmosphere or air with concentrations of iron oxide of about 20 to 30wt.%.     

Electronic structure and stability of Mg<Subscript>6</Subscript>Ti<Emphasis Type=Italic>M</Emphasis> (<Emphasis Type=Italic>M</Emphasis> = Mg,Al, Zn) and their hydrides

The influence of Al and Zn atoms on the stability of the Mg₇Ti compound and its hydride Mg₇TiH₁₆ has been studied theoretically. The calculations have been carried out in terms of the full-potential linearized augmented plane wave method. It has been demonstrated that the partial substitution of Al or Zn atoms for magnesium atoms leads to a decrease in the stability of the hydride and to an increase in the stability of the intermetallic compound.     

Investigations of dielectric enhancement in (Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>)<Subscript>1-x</Subscript>(TiO<Subscript>2</Subscript>)<Subscript>x</Subscript> ceramics prepared by laser-sintering technique

The maximum dielectric permittivity of Ti-doped Ta₂O₅ ceramics may reach 450 by a laser-sintering technique. The aim of this study is to investigate the mechanisms of the dielectric enhancement based on the unique structural and morphological properties of the laser-sintered ceramics. The reason for the dielectric enhancement is due to the crystal structure distortion in the high-temperature phase, the oriented grain growth taking place in a direction deviating from [001] in the laser-sintered ceramics. The concurrent nature of quenching effects, a sharp temperature gradient and mass transfer in liquid phase originated from laser high energy irradiation with strict directivity leads to the structural and morphological properties. PACS 81.40.Tv; 61.80.Ba; 77.22.-d; 77.22.Ch     

Preparation and properties of Fe and Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles in ZrO<Subscript>2</Subscript> matrix

Iron and magnetite nanoparticles in zirconium oxide matrix have been prepared by a heat treatment of a mixture of nanocrystalline iron oxide and zirconium oxide or zirconium hydride powders. Changes in the phase composition of the as-mixed powders during annealing in vacuum or in hydrogen were monitored using thermomagnetic curves. Structure and phase composition of the final products were characterized by X-ray powder diffraction and ⁵⁷Fe Mössbauer spectroscopy. Influence of the composition of the original mixture and quality of the annealing atmosphere on the final properties of the composites are discussed.     

Mössbauer spectra of Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cr<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>S solid solutions

Compounds in the CrS-FeS system over a wide range of compositions are investigated by Mössbauer spectroscopy. The analysis of the Mössbauer spectra demonstrates that the materials under investigation are substitutional solid solutions with a random distribution of chromium and iron atoms. The assumption is made that the observed broadened Zeeman sextets are superpositions of partial sextets corresponding to iron atoms with different nearest environments. The observed decrease in the hyperfine fields for the broadened sextets with an increase in the chromium content in the samples is in good agreement with a change in the concentration of the corresponding environments.     

Growth of polycrystalline LaNi<Subscript>1-x</Subscript>Co<Subscript>x</Subscript>O<Subscript>3</Subscript> (<Emphasis Type="BoldItalic">x</Emphasis> =0.3,0.5) thin films on Si(100) by pulsed laser deposition

Polycrystalline LaNi_1-xCo_xO₃ (x=0.5,0.3) thin films have been deposited on polished Si(100) substrates by pulsed laser deposition. The films are grown at 650 °C in ambient oxygen pressure of 0.4 mbar with an incident laser fluence of 1.5 J/cm² delivered by a KrF excimer laser. The lattice parameters of the as-grown films are slightly larger (0.05–0.4%) than those of the powders used to prepare the targets. The films exhibit weak texturing along the (012) direction. The low-temperature magnetic properties of the films, i.e. the coercive force, the remanence and the saturation magnetization, are enhanced compared to the powders. Furthermore, the x=0.3 film exhibits a low, almost temperature-independent resistivity above 200 K [(300 K)30 cm] and thus we propose it as a potential candidate material for electrode applications, e.g. in ferroelectric devices. PACS 68.55.-a; 73.61.-r; 81.15.Fg     

Electronic structure and stability of complex hydrides Mg<Subscript>2</Subscript><Emphasis Type="Italic">M</Emphasis>H<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> (<Emphasis Type="Italic">M</Emphasis> = Fe,Co)

This paper reports on the results of theoretical investigations carried out for the hydrides Mg₂FeH₆ and Mg₂CoH₅ and the mixed hydride Mg₂(FeH₆)_0.5(CoH₅)_0.5 in terms of the full-potential linearized augmented plane wave (FLAPW) method. It has been shown that the partial substitution of the Co atoms for the Fe atoms leads to a slight increase in the stability of the hydride, but, at the same time, makes it impossible to increase the stability of the alloy. The high stability of the hydrides under investigation has been explained by the strong bonding between atoms of the transition metal and hydrogen.     

Influence of Bi underlayer on the magnetic properties of Fe<Subscript>x</Subscript>Pt<Subscript>100-x</Subscript> (<Emphasis Type="BoldItalic">x</Emphasis> =<Emphasis Type="Bold">40</Emphasis>∼<Emphasis Type="Bold">58</Emphasis>) films

We have studied the effect of a Bi underlayer on ordering and coercivity H_c of Fe_xPt_100-x thin films (atomic content of Fe x=40∼58). We found that the Bi underlayer enhances H_c remarkably. After annealing at 400 °C for 20 min, a Bi/Fe₄₉Pt₅₁ film can realize an H_c as high as 1.07×10³ kA/m and a ratio of the remnant M_r to the saturated magnetization M_s as high as 0.93. The ordering process of FePt film was promoted by the diffusion of Bi atoms. Moreover, the Bi underlayer broadens the range of x for high H_c from 49∼55 to 43∼55. Interestingly, with Bi underlayer, the high H_c is affected by x to a less extent. PACS 75.50.Ss; 75.50.Vv; 75.60.Ej